It is an object of the present invention to provide an electrode capable of maintaining superior capacity retention without destruction of an electrode structure, even in the case of using an active material including silicon.
The present invention relates to “a binder for a lithium cell, the binder comprising polyacrylic acid cross-linked by a cross-linking agent selected from the compounds described in the general formulae [1] to [13] and the polymer described in the general formula [14] (provided that the one which includes a functional group-containing vinylidene fluoride-based polymer is excluded)”; a “composition for producing an electrode of a lithium cell, the composition comprising 1) an active material containing silicon, 2) a conductive assistant and 3) a cross-linked-type polyacrylic acid (provided that the one containing a functional group-containing vinylidene fluoride-based polymer is excluded)”; and an “electrode for a lithium cell, the electrode comprising 1) an active material containing silicon, 2) a conductive assistant, 3) a cross-linked-type polyacrylic acid, and 4) a current collector (provided that the one containing a functional group-containing vinylidene fluoride-based polymer is excluded)”.
|
9. A binder for a lithium cell comprising polyacrylic acid cross-linked by a cross-linking agent selected from the compounds described in the following general formulae [1] to [8], [10-1] to [10-4] and [11] to form a cross-linked polyacrylic acid, the cross-linked polyacrylic acid consisting of acrylic acid and the cross-linking agent as monomer components, provided that the binder which includes a functional group-containing vinylidene fluoride-based polymer is excluded, wherein an amount of the cross-linking agent is 0.007 to 0.5% by mol, to 1 mol of acrylic acid;
##STR00066##
wherein k represents an integer of 1 to 6,
##STR00067##
wherein R25 and R26 each independently represent a hydrogen atom or a methyl group, R20 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1],
wherein R17 represents an alkylene group having 1 to 6 carbon atoms, r represents an integer of 1 to 6, or the group represented by the following general formula [2-2]
wherein R18 and R19 each independently represent an alkylene group having 1 to 6 carbon atoms, t represents an integer of 1 to 12,
##STR00068##
wherein R1 to R6 and R61 each independently represent an alkylene group having 1 to 3 carbon atoms,
##STR00069##
wherein R7 to R10 each independently represent an alkylene group having 1 to 6 carbon atoms, 1 represents an integer of 1 to 6, in represents an integer of 0 to 6, v1 and v2 each independently represent an integer of 0 or 1,
##STR00070##
wherein R31 to R33 each independently represent a hydrogen atom, a vinyl group or a vinylketone group, and at least two or more groups thereof are a vinyl group or a vinylketone group,
##STR00071##
wherein R12 to R14 each independently represent an alkylene group having carbon 1 to 6 atoms,
##STR00072##
wherein Ar1 represents an aryl group having 6 to 10 carbon atoms, R15 represents an alkylene group having 1 to 6 carbon atoms, q represents an integer of 2 to 4,
##STR00073##
wherein Ar2 and Ar3 each independently represent an arylene group having 6 to 10 carbon atoms, R16 represents an alkylene group having 1 to 6 carbon atoms,
##STR00074##
wherein, represents an alkylene group having 1 to 6 carbon atoms.
1. A binder for a lithium cell comprising polyacrylic acid cross-linked by a cross-linking agent selected from the compounds described in the following general formulae [1] to [11] to form a cross-linked polyacrylic acid, the cross-linked polyacrylic acid consisting of acrylic acid and the cross-linking agent as monomer components, provided that the binder which includes a functional group-containing vinylidene fluoride-based polymer is excluded, wherein viscosity of the cross-linked polyacrylic acid is 30 to 10000 mPa ·S under 60 rpm of a rotational viscometer, or 10000 to 400000 mPa·S under 0.6 rpm of a rotational viscometer, provided that as viscosity measured in a dispersed solution of the cross-linked polyacrylic acid in water in a concentration of 1% by weight;
##STR00056##
wherein k represents an integer of 1 to 6,
##STR00057##
wherein R25 and R26 each independently represent a hydrogen atom or a methyl group, R20 represents an alkylene group having 1 to 20 carbon atoms, a group represented by the following general formula [2-1],
wherein R17 represents an alkylene group having 1 to 6 carbon atoms, r represents an integer of 1 to 6, or the group represented by the following general formula [2-2]
wherein R18 and R19 each independently represent an alkylene group having 1 to 6 carbon atoms, t represents an integer of 1 to 12,
##STR00058##
wherein R1 to R6 and R61 each independently represent an alkylene group having 1 to 3 carbon atoms,
##STR00059##
wherein R7 to R10 each independently represent an alkylene group having 1 to 6 carbon atoms, 1 represents an integer of 1 to 6, in represents an integer of 0 to 6, v1 and v2 each independently represent an integer of 0 or 1,
##STR00060##
wherein R31 to R33 each independently represent a hydrogen atom, a vinyl group or a vinylketone group, and at least two or more groups thereof are a vinyl group or a vinylketone group,
##STR00061##
wherein R12 to R14 each independently represent an alkylene group having carbon 1 to 6 atoms,
##STR00062##
wherein Ar1 represents an aryl group having 6 to 10 carbon atoms, R15 represents an alkylene group having 1 to 6 carbon atoms, q represents an integer of 2 to 4,
##STR00063##
wherein Ar2 and Ar3 each independently represent an arylene group having 6 to 10carbon atoms, R16 represents an alkylene group having 1 to 6 carbon atoms,
##STR00064##
wherein Ar4 represents an arylene group having 6 to 10 carbon atoms,
##STR00065##
wherein, R11 represents an alkylene group having 1 to 6 carbon atoms.
2. The binder according to
4. The binder according to
5. The binder according to
6. The binder according to
7. The binder according to
8. The binder according to
10. The binder according to
11. The hinder according to
12. The binder according to
13. The binder according to
|
This is a divisional of U.S. application Ser. No. 14/438,481, filed on Apr. 24, 2015, which is a 371 of PCT/JP2013/078996, filed on Oct. 25, 2013, which claims the benefit of priority over Japanese Application No. 2012-237026 filed on Oct. 26, 2012 and Japanese Application No. 2013-069859 filed on Mar. 28, 2013, the entire contents of which are incorporated herein by reference.
The present invention relates to a binder, a composition for producing an electrode and an electrode to be used in a lithium cell which uses the one containing silicon as an active material.
A lithium ion cell, as a secondary cell, has been utilized as a power source of various portable devices such as a mobile phone, however, in recent years, research and development of large size batteries assuming automotive applications and the like has become active. Therefore, it has become indispensable to further increase energy density of an existing lithium ion cell. Accordingly, use of a high capacity silicon material has attracted the attention, as an active material, instead of a carbon-based material. High capacity of silicon is considered to be due to providing higher electric capacity, as compared with the case of using carbon, because silicon can cause an alloying reaction with lithium electrochemically at room temperature.
However, silicon has been known to cause large volume change (enlarge to 3 times or more) on charge-discharge, when used as an active material. And, this volume change generates destruction of an electrode structure in charge-discharge, and leads to destruction of an electrode. As a result, it had a problem of shortening of cycle characteristics (lifetime) or the like. In addition, it had also a problem of larger self-discharge or the like, as compared with a graphite electrode.
On the other hand, various attempts of using a binder have been made, aiming at increasing capacity or enhancing stability performance of a cell (PATENT LITERATURE 1 and 2). However, these targeted active materials were mainly carbon materials, and does not aim at resolving the above-described problems in the case of using silicon.
PATENT LITERATURE 1: JP-A-2009-80971
PATENT LITERATURE 2: JP No. 4851092
It is an object of the present invention to provide a binder superior in solving such a problem as described above, and an electrode using the same.
The present inventors have variously studied a method for using a polymeric binder, as a solution of the above-described problems, in the case where silicon was used as an active material. As a result, it has been discovered that, by using, as a binder, a cross-linked polymer, among them, a polymer cross-linked the polyacrylic acid by a specific cross-linking agent, superior capacity retention rate can be obtained, without destruction of an electrode structure, even in the case of using an active material containing silicon, and have thus completed the present invention.
That is, the present invention relates to (1) “the binder for a lithium cell comprising polyacrylic acid cross-linked by a cross-linking agent selected from the compounds described in the following general formulae [1] to [13] and the polymer described in the general formula [14] (provided that the one which includes a functional group-containing vinylidene fluoride-based polymer is excluded);
##STR00001##
(wherein k represents an integer of 1 to 6.),
##STR00002##
[wherein R25 and R26 each independently represent a hydrogen atom or a methyl group, R20 represents an alkylene group having 1 to 20 carbon atoms, and a group represented by the following general formula [2-1],
R17—O
r [2-1]
(wherein R17 represents an alkylene group having 1 to 6 carbon atoms, r represents an integer of 1 to 6.), or the group represented by the following general formula [2-2]
R18—O
tR19— [2-2]
(wherein R18 and R19 each independently represent an alkylene group having 1 to 6 carbon atoms, t represents an integer of 1 to 12.)],
##STR00003##
(wherein R1 to R6 and R61 each independently represent an alkylene group having 1 to 3 carbon atoms.),
##STR00004##
(wherein R7 to R10 each independently represent an alkylene group having 1 to 6 carbon atoms, 1 represents an integer of 1 to 6, m represents an integer of 0 to 6, v1 and v2 each independently represent an integer of 0 or 1.),
##STR00005##
(wherein R31 to R38 each independently represent a hydrogen atom, a vinyl group or a vinylketone group, and at least two or more groups thereof are a vinyl group or a vinylketone group.),
##STR00006##
(wherein R12 to R14 each independently represent an alkylene group having 1 to 6 carbon atoms.),
##STR00007##
(wherein Ar1 represents an aryl group having 6 to 10 carbon atoms, R15 represents an alkylene group having 1 to 6 carbon atoms, q represents an integer of 2 to 4.),
##STR00008##
(wherein Ar2 and Ar3 each independently represent an arylene group having 6 to 10 carbon atoms, R16 represents an alkylene group having 1 to 6 carbon atoms.),
##STR00009##
(wherein Ar4 represent an arylene group having 6 to 10 carbon atoms.),
##STR00010##
(wherein p represents an integer of 0 to 6.),
##STR00011##
(wherein, R11 represents an alkylene group having 1 to 6 carbon atoms.),
##STR00012##
[wherein R21 represents an alkylene group having 1 to 6 carbon atoms which has or does not have a substituent, an arylene group having 6 to 10 carbon atoms which has or does not have a substituent, or a group represented by the following general formula [12-A]
##STR00013##
(wherein R35 represents an alkyl group having 1 to 6 carbon atoms, R36 represents an alkyl group having 1 to 6 carbon atoms, Ar5 represents an arylene group having 6 to 10 carbon atoms which may have b pieces of R35 as substituents, b represents an integer of 0 to 4.), or the group represented by the following general formula [12-B]
##STR00014##
(wherein R37 represents an alkylene group having 1 to 6 carbon atoms, R35, R36, Ar5 and b are the same as described above.)],
##STR00015##
[wherein R22 each independently represent an alkyl group having 1 to 6 carbon atoms which has or does not have a substituent, an aryl group having 6 to 10 carbon atoms which has or does not have a substituent, or the group represented by the following general formula [13-A]
##STR00016##
(wherein R40 represents an alkyl group having 1 to 6 carbon atoms, R41 represents an alkylene group having 1 to 6 carbon atoms, Ar6 represents an arylene group having 6 to 10 carbon atoms which have c pieces of R40 as substituents, and c represents an integer of 0 to 5.)],
##STR00017##
[wherein R23 represents an alkylene group having or not having a substituent a substituent, and 1 to 6 carbon atoms, an arylene group having or not having a substituent a substituent, and carbon atoms of 6 to 10, or a group represented by the following general formula [14-A] or [14-B]
##STR00018##
(wherein R30 represents an alkyl group having 1 to 6 carbon atoms, R31 represents an alkylene group having 1 to 6 carbon atoms, Ar7 represents an arylene group having 6 to 10 carbon atoms which may have a piece of R30 as substituents, a represents an integer of 0 to 4.), or the group following general formula [14-C]
##STR00019##
(wherein R32 represents an alkylene group having 1 to 6 carbon atoms, R30, R31, Ar7, and a are the same as described above.), s represents an integer of 10 to 10000.]”, (2) “the composition for producing an electrode of a lithium cell comprising 1) an active material containing silicon, 2) a conductive assistant and 3) a cross-linked-type polyacrylic acid (provided that the one containing a functional group-containing vinylidene fluoride-based polymer is excluded)” and (3) “the electrode for a lithium cell comprising 1) an active material containing silicon, 2) a conductive assistant, 3) a cross-linked-type polyacrylic acid, and 4) a current collector (provided that the one containing a functional group-containing vinylidene fluoride-based polymer is excluded)”.
By producing a lithium electrode using the binder of the present invention, such an electrode that an electrode structure is not destroyed can be provided, even in the case of using an active material including silicon. In addition, said electrode makes possible to provide a cell which is capable of maintaining high capacity over a long period of time, because of exhibiting high capacity retention rate, even in the case of repeated charge-discharge. Further, said electrode exhibits high coulombic efficiency in the initial cycle, as well as exerts effect of early stabilization of coulombic efficiency in the 2nd and the subsequent cycles.
[Compounds Described in the General Formulae [1] to [13], and a Polymer Described in the General Formulae [14]]
“k” in the general formula [1] pertaining to the present invention is usually 1 to 6, preferably 1 to 3, and more preferably 1.
Preferable specific examples of the group shown by the general formula [1] pertaining to the present invention include, for example, the groups shown by the following formulae [1-1] to [1-6],
##STR00020##
and the like, and the one represented by the formula [1-1] is particularly preferable.
The alkylene group having 1 to 20 carbon atoms in R20 of the general formula [2] pertaining to the present invention may be a straight chain, a branched, or a cyclic group, and the straight chain group is preferable, the one having 1 to 12 carbon atoms is preferable. Specifically, they include, for example, a methylene group, an ethylene group, a n-propylene group, an isopropylene group, a n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a n-pentylene group, an isopentylene group, a sec-pentylene group, a tert-pentylene group, a neopentylene group, a n-hexylene group, an isohexylene group, a sec-hexylene group, a tert-hexylene group, a n-heptylene group, an isoheptylene group, a sec-heptylene group, a tert-heptylene group, a n-octylene group, a sec-octylene group, a tert-octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, an icosylene group, a cyclopropylene group, a cyclopentylene group, a cyclohexylene group a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, a cyclododecylene group, cyclotridecylene group, a cyclohexadecylene group, a cyclooctadecylene group, a cycloicosylene group, or the like, among them, a methylene group, an ethylene group, a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, n-heptylene group, a n-octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, or the like are preferable.
The alkylene group having 1 to 6 carbon atoms in R17, R18 and R19 of the general formula [2-1] or [2-2] pertaining to the present invention may be a straight chain, a branched, or a cyclic group, and the straight chain group is preferable. In addition, 1 to 3 carbon atoms are preferable, 2 to 3 carbon atoms are more preferable, and 2 carbon atoms are particularly preferable. Specifically, they include for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a methylmethylene group, a methylethylene, group, an ethylmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, or the like, and a methylene group, an ethylene group or a propylene group are preferable, and an ethylene group and a propylene group are more preferable.
“r” in the general formula [2-1] pertaining to the present invention is preferably an integer of 2 to 6, and more preferably an integer of 4 to 6.
“t” in the general formula [2-2] pertaining to the present invention is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and still more preferably 1 to 3.
Preferable specific examples of the group shown by the general formula [2-1] pertaining to the present invention include, for example, the groups represented by the following formulae [2-1-1] to [2-1-3],
CH2—O
r [2-1-1]
C2H4—O
r [2-1-2]
C3H6—O
r [2-1-3]
(wherein, r is the same as described above.) and the like, among them, the group shown by [2-1-2] is particularly preferable.
Preferable specific examples of the group shown by the general formula [2-2] pertaining to the present invention include, for example, the groups shown by the following formulae [2-2-1] to [2-2-3]
CH2—O
tCH2— [2-2-1]
CH2H4—O
tCH2H4— [2-2-2]
C3H6—O
tC3H6— [2-2-3]
(wherein t is the same as described above.) and the like.
Preferable specific examples of the group represented by the general formula [2] pertaining to the present invention include, for example, the groups represented by the following formulae [2-01] to [2-14], and among them, the general formulae [2-05] to [2-07] and [2-12] to [2-14] are preferable, the general formulae [2-06] and [2-13] are more preferable, and [2-06] is particularly preferable.
##STR00021##
(wherein u represents an integer of 1 to 6, and 4 to 6 is preferable, and 6 are more preferable.)
##STR00022##
(wherein r is the same as described above.)
##STR00023##
(wherein t is the same as described above.)
##STR00024##
(wherein u represents an integer of 1 to 6, and 4 to 6 is preferable, and 6 are more preferable.)
##STR00025##
(wherein r is the same as described above.)
##STR00026##
(wherein t is the same as described above.)
The alkylene group having 1 to 3 carbon atoms in R1 to R6, and R61 of the general formula [3] pertaining to the present invention may be a straight chain or a branched group, and the straight chain group is preferable, the one having 1 to 2 carbon atoms is preferable, and 1 carbon number is more preferable. Specifically, there are included, for example, a methylene group, an ethylene group, a trimethylene group, or the like, a methylene group, and an ethylene group are preferable, and a methylene group is more preferable.
Preferable specific examples of the group represented by the general formula [3] pertaining to the present invention include, for example, the groups represented by the following formulae [3-1] to [3-3],
##STR00027##
and the like, and the formula [3-1] is particularly preferable.
The alkylene group having 1 to 6 carbon atoms in R7 to R10 of the general formula a [4] pertaining to the present invention includes the same one as the alkylene group having 1 to 6 carbon atoms in R17 of the above-described general formula [2-1].
“l” represents an integer of 1 to 6, and integer of 1 to 4 is preferable. In the case where “l” is 2 or more, plural R7 may be the same or different.
“m” represents an integer of 0 to 6, and integer of 1 to 3 is preferable, and 1 is more preferable. In the case where “l” is 2 or more, plural R7 may be the same one or the different one. In the case where “m” is 2 or more, plural R8 may be the same one or the different one. It should be noted that in the case where “m” is 0, —R8O— represents a bond. That is, it represents direct binding of adjacent —O— and —(R10)v2-. Hereafter, the “bond” represents similar meaning.
“v1” and “v2” each independently represents an integer of 0 or 1. It should be noted that in the case where “v1” is 0, —R9— represents a bond, and in the case where “v2” is 0, —R10— represents a bond.
Specific examples of the compound shown by the general formula [4] pertaining to the present invention include, for example, the following general formula [4′] or the general formula [4″], and particularly the general formula [4′] is preferable.
##STR00028##
[wherein R7′ and R8′ represent a methylene group, an ethylene group, an n-propylene group (preferably, an ethylene group), 1′ represents an integer of 1 to 2, m′ represents an integer of 0 to 2.]
##STR00029##
(wherein R7″ represents a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group, and l″ represents an integer of 1 to 4.)
Preferable specific examples of the general formula [4] include, for example, the compounds shown by the following general formulae [4-1] to [4-10],
##STR00030##
and the like, and among them, formulae [4-1] to [4-4] are preferable.
In R31 to R38 of the general [5] pertaining to the present invention, at least two or more groups are vinyl groups or vinylketone groups, 5 to 8 groups are preferably vinyl groups or vinylketone groups, and 5 to 7 groups are more preferably vinyl groups or vinylketone groups.
Preferable specific examples of the compound shown by the general formula [5] pertaining to the present invention include, for example, the compounds shown by the following general formulae [5-1] to [5-6]
##STR00031##
##STR00032##
and the like.
The alkylene group having 1 to 6 carbon atoms in R12 to R14 of the general formula [6] pertaining to the present invention includes the same one as the alkylene group having 1 to 6 carbon atoms in R17 of the above-described general formula [2-1]. As a preferable group in R12 and R14, a methylene group and an ethylene group are preferable, and an ethylene group is more preferable. In R13, a cyclopentylene group and a cyclohexylene group are preferable, and a cyclohexylene group is more preferable.
Preferable specific examples of the compound shown by the general formula [6] pertaining to the present invention include, for example, the compounds represented by the following general formulae [6-1] to [6-3],
##STR00033##
and the like, and among them, the formula [6-1] is preferable.
The alkylene group having 1 to 6 carbon atoms in R15 of the general formula [7] pertaining to the present invention includes the same one as the alkylene group having 1 to 6 carbon atoms in R17 of the above-described general formula [2-1]. As a preferable group, a methylene group and an ethylene group are preferable, and a methylene group is more preferable.
The aryl group in Ar1 of the general formula [7] pertaining to the present invention includes usually the one having 6 to 10 carbon atoms, and preferably the one having carbon atoms of 6, specifically includes, for example, a phenyl group, a naphthyl group, and the like, and a phenyl group is preferable.
“q” represents an integer of 2 to 4, preferably is an integer of 3 to 4.
Preferable specific examples of the compound represented by the general formula [7] pertaining to the present invention include, for example, and the compounds shown by the following general formulae [7-1] to [7-2]
##STR00034##
and the like.
The arylene group in Ar2 or Ar3 of the general formula [8] pertaining to the present invention includes usually the one having 6 to 10 carbon atoms, preferably the one having 6 carbon atoms, specifically includes, for example, a phenylene group, a naphthylene group, or the like, and a phenylene group is preferable.
The alkylene group having 1 to 6 carbon atoms in R16 of the general formula [8] pertaining to the present invention includes the same one as the alkylene group having 1 to 6 carbon atoms in R17 of the above-described general formula [2-1]. As the preferable group, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
Preferable specific examples of the compound represented by the general formula [8] pertaining to the present invention include, for example, and the compounds shown by the following general formulae [8-1] to [8-2],
##STR00035##
and the like, and the general formula [8-1] is preferable.
The arylene group in Ar4 of the general formula [9] pertaining to the present invention includes the same one as the arylene group in Ar2 or Ar3 of the general formula [8], and the preferable one is also the same.
Preferable specific examples of the compound represented by the general formula [9] pertaining to the present invention include, for example, and the compounds represented by the following general formulae [9-1] to [9-2],
##STR00036##
and the like, and the general formula [9-1] is preferable.
“p” in the general formula [10] pertaining to the present invention is preferably 0 to 2, and 0 is particularly preferable.
Preferable specific examples of the compound represented by the general formula [10] pertaining to the present invention include, for example, the compounds shown by the following general formulae [10-1] to [10-4],
##STR00037##
and the like, and the general formula [10-1] is preferable.
The alkylene group having 1 to 6 carbon atoms in R11 of the general formula [11] pertaining to the present invention includes the same one as the alkylene group having 1 to 6 carbon atoms in R17 of the above-described general formula [2-1]. As the preferable one, a methylene group, an ethylene group, and an n-propylene group are preferable, a methylene group is more preferable.
Preferable specific examples of the compound represented by the general formula [11] pertaining to the present invention include, for example, the compounds represented by the following general formulae [11-1] to [11-3],
##STR00038##
and the like, and the general formula [11-1] is preferable.
The alkylene group having 1 to 6 carbon atoms in R21 of the general formula [12] pertaining to the present invention may be any of a straight chain, a branched or a cyclic group, and includes, specifically, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a methylmethylene group, a methylethylene group, an ethylmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, or the like.
The arylene group having 6 to 10 carbon atoms in R21 of the general formula [12] pertaining to the present invention includes the one having 6 carbon atoms preferably, and specifically includes, for example, a phenylene group, a naphthylene group, or the like, and a phenylene group is preferable.
The alkyl group having 1 to 6 carbon atoms in R35 of the general formulae [12-A] and [12-B] pertaining to the present invention may be any of a straight chain, a branched or a cyclic group, and the straight chain group is preferable. Specifically, for example, they include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, or the like.
As the alkylene group having 1 to 6 carbon atoms in R36 of the general formulae [12-A] and [12-B] pertaining to the present invention, it includes the same alkylene group having 1 to 6 carbon atoms in the above-described R21.
As the arylene group having 6 to 10 carbon atoms in Ar5 of the general formulae [12-A] and [12-B] pertaining to the present invention, it includes the same arylene group having 6 to 10 carbon atoms in the above-described R21.
“b” in the general formulae [12-A] and [12-B] pertaining to the present invention represents an integer of 0 or 1. In the case where b is 0, it means that the arylene group of Ar5 does not have a substituent.
As the alkylene group having 1 to 6 carbon atoms in R37 of the general formula [12-B] pertaining to the present invention, it includes the same alkylene group having 1 to 6 carbon atoms in the above-described R21.
Preferable specific examples of the general formula [12] include the following general formulae [12-1] to [12-4]
##STR00039##
(wherein R35 and b are the same as described above.)
##STR00040##
(wherein R35, R36 and b are the same as described above.)
##STR00041##
(wherein R35, R36, R37 and b are the same as described above.)
##STR00042##
(wherein R37 is the same as described above.) and the like.
As the alkyl group having 1 to 6 carbon atoms in R22 of the general formula [13] pertaining to the present invention, it includes the same alkyl group having 1 to 6 carbon atoms in the above-described R35 of the general formula [12-A] pertaining to the above-described present invention.
As the aryl group having 6 to 10 carbon atoms in R22 of the general formula [13] pertaining to the present invention, it includes the same aryl group having 6 to 10 carbon atoms in the Ar1 of the general formula [7] pertaining to the above-described present invention, and also the substituent includes the same one.
As the alkyl group having 1 to 6 carbon atoms in R40 of the general formula [13-A] pertaining to the present invention, it includes the same alkyl group having 1 to 6 carbon atoms in the R35 of the general formula [12-A].
As the alkylene group having 1 to 6 carbon atoms in R41 of the general formula [13-A] pertaining to the present invention, it includes the same alkylene group having 1 to 6 carbon atoms in the above-described R21.
As the aryl group having 6 to 10 carbon atoms in Ar6 of the general formula [13-A] pertaining to the present invention, it includes the same aryl group having 6 to 10 carbon atoms in the above-described R22.
“c” in the general formula [13-A] pertaining to the present invention represents an integer of 0 to 5, and preferably 0 to 2. In the case where c is 0, it means that the aryl group of Ar6 does not have a substituent.
Preferable specific examples of the general formula [13] include, for example, the compounds represented by the following general formulae [13-1], [13-2] and the like.
##STR00043##
(wherein R40 represents the alkyl group having 1 to 6 carbon atoms, and c represents an integer of 0 to 4.), among them, the general formula [13-1] is preferable. Among the general formula [13-1], R40 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or the like, and an isopropyl group is more preferable. Among the general formula [13-1], the one in which c is an integer of 1 to 3 is preferable, and 2 is more preferable.
The alkylene group having 1 to 6 carbon atoms in R23 of the general formula [14] pertaining to the present invention includes the same alkylene group having 1 to 6 carbon atoms in R21 of the general formula [12] pertaining to the above-described present invention, and also the substituent includes the same one.
The arylene group having 6 to 10 carbon atoms in R23 of the general formula [14] pertaining to the present invention includes the same arylene group having 6 to 10 carbon atoms in R21 of the general formula [12] pertaining to the above-described present invention, and also the substituent includes the same one.
The alkyl group having 1 to 6 carbon atoms in R30 of the general formulae [14-A] to [14-C] pertaining to the present invention includes the same alkyl group having 1 to 6 carbon atoms in R35 of the general formula [12-A].
The alkylene group having 1 to 6 carbon atoms in R31 of the general formulae [14-A] to [14-C] pertaining to the present invention includes the same alkylene group having 1 to 6 carbon atoms in the above-described R21.
The arylene group having 6 to 10 carbon atoms in Ar7 of the general formulae [14-A] to [14-C] pertaining to the present invention includes the same arylene group having 6 to 10 carbon atoms in the above-described R21.
“a” in the general formulae [14-A] to [14-C] pertaining to the present invention represents an integer of 0 or 1. In the case where a is 0, it means that the aryl group of Ar7 does not have a substituent.
The alkylene group having 1 to 6 carbon atoms in R32 of the general formula [14-C] pertaining to the present invention includes the same alkylene group having 1 to 6 carbon atoms in the above-described R21.
R23 of the general formula [14] pertaining to the present invention is preferably the alkylene group having a substituent and carbon atoms of 1 to 6, the alkylene group having no substituent and carbon atoms of 1 to 6, the arylene group having a substituent and carbon atoms of 6 to 10, or the arylene group having no substituent and carbon atoms of 6 to 10, and in particular, the arylene group having a substituent and carbon atoms of 6 to 10 is more preferable, and the arylene group having an alkyl group as a substituent and carbon atoms of 6 to 10 is particularly preferable.
“s” in the general formula [14] pertaining to the present invention is usually 10 to 10000, preferably 10 to 1000, and more preferably 10 to 100.
Preferable specific examples of the general formula [14] include, for example, and the following general formulae [14-1] to [14-5]
##STR00044##
(wherein R30 represents the alkyl group having 1 to 6 carbon atoms, and a represents an integer of 0 to 4, and s is the same as described above.)
##STR00045##
(wherein R31 represents the alkylene group having 1 to 6 carbon atoms. R30, a and s are the same as described above.)
##STR00046##
(wherein R30, R31, a and s are the same as described above.)
##STR00047##
(wherein R30, R31, a and s are the same as described above. However, two R31 are each independent and may be different groups.)
N═C═N—R33
S [14-5]
(wherein R33 represents the alkylene group having 1 to 6 carbon atoms, and s is the same as described above), among them, the general formula [14-1] is preferable, and more specifically, include, the following general formulae [14-1-1] to [14-1-3]
##STR00048##
(wherein s is the same as described above) and the like, and the general formula [14-1-1] is preferable.
As the cross-linking agent pertaining to the present invention, among compounds described in the general formulae [1] to [13] and the polymer described in the general formula [14], compounds described in the general formula [2], the general formula [3], the general formula [4], the general formula [9], the general formula [10] and the general formula [11], as well as the polymer described in the general formula [14] are preferable, compounds described in the general formula [2], the general formula [3], the general formula [4] and the general formula [10] are more preferable, and among them, the compound described in the general formula [4] is preferable.
[Binder for Lithium Cell]
The binder for a lithium cell of the present invention is the one composed of polyacrylic acid (hereafter it may be abbreviated as the cross-linked-type polyacrylic acid pertaining to the present invention) cross-linked by a cross-linking agent selected from compounds described in the above-described general formulae [1] to [13] and the polymer described in the general formula [14]. It should be noted that the binder for a lithium cell of the present invention includes also the one composed of polyacrylic acid which is not cross-linked in storage, and is cross-linked in usage by a cross-linking agent selected from the compound described in the above-described general formula [12] and the general formula [13] and the polymer described in the general formula [14].
Cross-linked-type polyacrylic acid pertaining to the present invention may be neutralized. In other words, a part or all of the carboxyl groups in the cross-linked-type polyacrylic acid may be a salt. As the neutralized cross-linked-type polyacrylate, the one neutralized with an alkaline metal such as sodium hydroxide, lithium hydroxide, potassium hydroxide is preferable, and the one neutralized with sodium hydroxide is more preferable. Specifically, cross-linked-type poly(sodium acrylate), cross-linked-type poly(lithium acrylate), cross-linked-type poly(potassium acrylate) or the like is preferable, and among them, cross-linked-type poly(sodium acrylate) is more preferable. Use of such a neutralized cross-linked-type polyacrylic acid makes possible to further enhance electric characteristics of an electrode. Degree of neutralization in this case is usually 60 to 100%, preferably 70 to 100%, and more preferably 70 to 90%. In addition, the cross-linked-type polyacrylate is obtained by neutralizing the polyacrylic acid which is subjected to polymerization reaction and cross-linking reaction, or the polyacrylic acid which is subjected to a cross-linking reaction. Alternatively, it is also obtained, after neutralization of straight chain (not cross-linked) acrylic acid, by subjecting it to a polymerization reaction and a cross-linking reaction, or after neutralization of straight chain (not cross-linked) acrylic acid, by subjecting it to a cross-linking reaction. Among them, it is preferable to neutralize polyacrylic acid which is subjected to a polymerization reaction and a cross-linking reaction or polyacrylic acid which is subjected to a cross-linking reaction. It should be noted that the cross-linked-type polyacrylate may be prepared in accordance with a neutralization method known per se.
As for viscosity of the cross-linked-type polyacrylic acid pertaining to the present invention, the lower limit thereof is usually 30 mPa·S and preferably 40 mPa·S under 60 rpm of a rotational viscometer, and the upper limit thereof is 800000 mPa·S, preferably 450000 mPa·S and more preferably 400000 mPa·S under 0.6 rpm of a rotational viscometer. It should be noted that the upper limit viscosity under 60 rpm of the rotational viscometer is 10000 mPa·S, and the lower limit viscosity under 0.6 rpm of the rotational viscometer is 10000 mPa·S. Said viscosity is a value measured at 20 to 25° C. with a B-type viscometer on a dispersed (suspended) solution of the cross-linked-type polyacrylic acid in water in a concentration of 1% by weight.
As the binder for a lithium cell of the present invention, the one in which cross-linked-type polyacrylic acid is dissolved or dispersed in a solvent is preferable, and said solvent includes, for example, N-methyl-2-pyrrolidone(NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, γ-butyronitrile, toluene, methyl ethyl ketone, ethyl acetate, dioxane, or the like, and among them, NMP is preferable. Concentration of the cross-linked-type polyacrylic acid in the binder for a lithium cell may be set as appropriate according to the concentration to be used in electrode preparation, and usually it is 1 to 30 mg/mL, preferably 1 to 10 mg/mL.
The cross-linked-type polyacrylic acid pertaining to the present invention can be prepared by subjecting acrylic acid and the compounds of the general formulae [1] to [11] to polymerization reaction and cross-linking reaction, or by subjecting polyacrylic acid and the compound of the general formula [12], the compound of the general formula [13], or a polymer of the general formula [14] to a cross-linking reaction. Said polymerization reaction and cross-linking reaction may be performed in accordance with a method known per se, and in the case where they are subjected to the polymerization reaction and the cross-linking reaction, the polymerization reaction and the cross-linking reaction may be performed in two stages, or the polymerization reaction and the cross-linking reaction may be performed at the same time. In addition, depending on a kind of a polymerization initiator or a cross-linking agent, or a method of polymerization or cross-linking, it may be prepared by subjecting them to the reaction by performing heating or ultraviolet ray irradiation. Reaction time, in which heating is not applied in the cross-linking reaction, is usually 0.1 to 10 hours and preferably, 0.1 to 5 hours. In addition, when heating is applied in the cross-linking reaction, it is reacted usually at 30 to 200° C., preferably at 70 to 180° C., and more preferably at 100 to 160° C., for usually 0.1 to 10 hours and preferably 0.1 to 5 hours. In the case of neutralizing the cross-linked-type polyacrylic acid, it may be neutralized with NaOH, LiOH, KOH or the like, after the cross-linking reaction.
The cross-linked-type polyacrylic acid pertaining to the present invention is prepared, specifically, as described below.
That is, it is prepared by dissolving or dispersing acrylic acid and the above-described compounds of the general formulae [1] to [11] in a suitable solvent, in the presence of the polymerization initiator, and subjecting them to a reaction for 0.1 to 10 hours, if necessary, under heating at 30 to 200° C., or cooling at 20 to −80° C. In addition, by further adding 0.6 to 1 mol of NaOH, LiOH, KOH or the like, to 1 mol of the carboxyl group of the obtained cross-linked-type polyacrylic acid, it may be converted to the cross-linked-type polyacrylate. As a solvent to be used in this reaction, a solvent which dissolves or disperses the above-described cross-linked-type polyacrylic acid, or the like is included. The polymerization initiator is not especially limited as long as it is the well-known one, and includes, for example, a radical polymerization initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, t-butylhydroperoxide, hydrogen peroxide, 2,2′-azobisisobutyronitrile, 4,4′-azobis(4-cyanopentanoic acid), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), triethylborane; and an ionic polymerization initiator such as n-butyl lithium, s-butyl lithium, t-butyl lithium, or the like. Use amount of the polymerization initiator may be set appropriately from a range of 0.001 to 1 g, to 1 mol of acrylic acid. In addition, use amount of compounds of the general formulae [1] to [11] is usually 0.001 to 10% by mol, preferably 0.01 to 1% by mol, more preferably 0.05 to 0.5% by mol, and still more preferably 0.1 to 0.3% by mol, to 1 mol of acrylic acid. After that, in the case of neutralizing polyacrylic acid, neutralization processing is performed by adding, for example, 60 to 100% by mole of sodium hydroxide, to 1 mol of the carboxylic acid in polyacrylic acid.
In addition, the cross-linked-type polyacrylic acid pertaining to the present invention is prepared by dissolving or dispersing polyacrylic acid and the compound of the general formula [12] or [13], or the polymer of the general formula [14], in a suitable solvent, and subjecting them to a reaction for 0.1 to 10 hours, if necessary, under heating at 30 to 200° C. As the solvent to be used here, the same solvent as used in the above-described preparation method is included. Use amount of the compound of the general formulae [12] to [13], or the polymer of the general formula [14] is usually, 0.01 to 40% by weight, preferably 0.01 to 20% by weight and more preferably 0.1 to 10% by weight, to weight of polyacrylic acid. Weight average molecular weight of polyacrylic acid to be used in this reaction is usually 1,000 to 10,000,000, and preferably 10,000 to 5,000,000. After that, in the case of neutralizing polyacrylic acid, neutralization processing is performed by adding, for example, 60 to 100% by mole of sodium hydroxide, to 1 mol of the carboxylic acid in polyacrylic acid.
[Active Material Containing Silicon]
The active material pertaining to the present invention contains silicon, and the active material other than silicon includes carbon, germanium, tin, lead, zinc, aluminum, indium, or the like, and among them, carbon is preferable.
The above-described silicon includes, in addition to silicon, a silicon oxide such as SiO, silicon bound to a metal (SiM: M is a metal such as magnesium, iron, calcium, cobalt, nickel, or boron), or the like.
The above-described carbon includes, for example, a graphite-based carbon material (graphite) such as natural graphite, artificial graphite, expanded graphite; carbon black, activated carbon, carbon fiber, cokes, soft carbon, hard carbon, or the like. The preferable one includes the graphite such as natural graphite, artificial graphite, and expanded graphite. Said natural graphite includes, for example, scale-like graphite, bulk graphite, or the like. Said artificial graphite includes bulk graphite, vapor phase epitaxy graphite, scale-like graphite, or fibrous graphite.
Average particle size of the active material pertaining to the present invention differs depending on a kind of the active material. It is usually 1 nm to 100 μm, preferably 1 nm to 50 μm and more preferably 1 nm to 20 μm.
Content of silicon in the active material pertaining to the present invention is usually 10 to 60% by weight, and preferably 20 to 50% by weight.
[Conductive Assistant]
The conductive assistant pertaining to the present invention includes, for example, carbon black such as acetylene black, Ketjen black, furnace black, thermal black, and among them, acetylene black and Ketjen black are preferable, and acetylene black is more preferable.
[Composition for Producing Electrode]
The composition for producing an electrode of the present invention comprises 1) the active material containing silicon pertaining to the present invention, 2) the conductive assistant pertaining to the present invention and 3) the cross-linked-type polyacrylic acid pertaining to the present invention, and does not comprising a functional group-containing vinylidene fluoride-based polymer. Said composition may be for preparation of positive electrode, or for preparation of negative electrode, and it is preferable to be for preparation of negative electrode.
Content of the active material containing silicon pertaining to the present invention, in the composition for producing an electrode of the present invention, is 60 to 98% by weight, more preferably 70 to 98% by weight, and still more preferably 80 to 98% by weight, to weight of the composition for producing an electrode not including a solvent.
Content of the conductive assistant pertaining to the present invention, in the composition for producing an electrode of the present invention, is 1 to 20% by weight, more preferably 1 to 15% by weight, and still more preferably 1 to 10% by weight, to weight of the composition for producing an electrode not including a solvent.
Content of the cross-linked-type polyacrylic acid pertaining to the present invention, in the composition for producing an electrode of the present invention, is 1 to 30% by weight, more preferably 1 to 20% by weight, still more preferably 1 to 15% by weight, and still further preferably 1 to 10% by weight to weight of the composition for producing an electrode not including a solvent. By making the cross-linked-type polyacrylic acid contained within this range, the active material and the conductive assistant can be dispersed uniformly on a current collector in producing of an electrode, as well as destruction of an electrode structure can be prevented, even on silicon expansion.
The composition for producing an electrode of the present invention may comprise, for example, a supporting salt, an ion conductive polymer, a binder (excluding the cross-linked-type polyacrylic acid pertaining to the present invention), and the like, other than the active material containing silicon, the conductive assistant and the cross-linked-type polyacrylic acid pertaining to the present invention. Said supporting salt includes Li(C2F5SO2)2N(LiBETI), LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, or the like. Said ion conductive polymer includes, for example, polyethylene oxide (PEO)-based, and polypropylene oxide (PPO)-based polymers. The above-described binder includes, for example, polyfluorovinylidene (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), styrene-butadiene copolymer (SBR), an acrylonitrile-butadiene copolymer (NBR), polyacrylonitrile (PAN), ethylene-vinyl alcohol copolymer (EVOH), polyurethane, polyacrylate, polyvinyl ether, polyimide, or the like. Content of these supporting salt, ion conductive polymer, and binder may be set in accordance with amount to be used usually in this field.
The composition for producing an electrode of the present invention is obtained by mixing the active material containing silicon pertaining to the present invention, the conductive assistant pertaining to the present invention, and the cross-linked-type polyacrylic acid pertaining to the present invention, in a suitable solvent, so as to attain the above-described concentration range. Said solvent includes, for example, N-methyl-2-pyrrolidone(NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, γ-butyrolactone toluene, methyl ethyl ketone, ethyl acetate, dioxane, or the like, and NMP is preferable.
In the case where the compound shown by the general formula [12] or [13], or the polymer of the general formula [14] is used, as the cross-linking agent of polyacrylic acid, the composition for producing an electrode of the present invention may be produced by dispersing or dissolving the active material containing silicon pertaining to the present invention, the conductive assistant pertaining to the present invention, and polyacrylic acid, as well as the compound represented by the general formula [12] or [13], or the polymer shown by the general formula [14], in a suitable solvent as described above, and then by subjecting them to a cross-linking reaction. That is, the composition for producing an electrode may be produced at the same time as cross-linking of polyacrylic acid by the cross-linking agent (the compound shown by the general formula [12] or [13], or the polymer shown by the general formula [14]). As for condition or the like of the above-described cross-linking reaction, the same one as described in the preparation method for the cross-linked-type polyacrylic acid pertaining to the present invention of [Binder for lithium cell] is included. Weight average molecular weight of polyacrylic acid to be used in this occasion is usually 1,000 to 10,000,000, and preferably 10,000 to 5,000,000. Use amount of polyacrylic acid in this case may be set appropriately, so that the obtained cross-linked-type polyacrylic acid is within the above-described range. In addition, use amount of the cross-linking agent is usually 0.01 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight, to said polyacrylic acid. In addition, in the case of neutralizing the cross-linked-type polyacrylic, acid in the above-described method, the composition for producing an electrode of the present invention may be produced by using polyacrylic acid neutralized in advance, instead of polyacrylic acid.
[Current Collector]
A current collector pertaining to the present invention is composed of a foil, a mesh, an expanded grid (an expanded metal), a punched metal or the like using a conductive material such as nickel, copper, stainless steel (SUS), or the like. Sieve opening of the mesh, wire diameter, number of the mesh, and the like are not especially limited, and the one known in prior art can be used. Preferable thickness of the current collector is 5 to 30 μm. However, the current collector having thickness outside this range may be used.
Size of the current collector is determined depending on the use applications of a cell. In the case of producing a large size electrode to be used in a large size cell, the current collector having large area is used. In the case of manufacturing a small size electrode to be used in a small size cell, the current collector having small area is used.
[Electrode of the Present Invention]
The electrode of the present invention comprises 1) the active material containing silicon pertaining to the present invention, 2) the conductive assistant pertaining to the present invention, 3) the cross-linked-type polyacrylic acid pertaining to the present invention, and 4) the current collector pertaining to the present invention, and does not comprise a functional group-containing vinylidene fluoride-based polymer. Specifically, it comprises the current collector pertaining to the present invention, and the active material layer (the composition for producing an electrode pertaining to the present invention) including, the active material containing silicon pertaining to the present invention, the conductive assistant pertaining to the present invention and the cross-linked-type polyacrylic acid pertaining to the present invention, formed at the surface thereof. The electrode of the present invention can be used either as a negative electrode or a positive electrode, and, it is preferable to be used as a negative electrode.
In the above-described active material layer, the electrode of the present invention is superior in reversibility because the cross-linked-type polyacrylic acid disperses uniformly the active material containing silicon and the conductive assistant, and maintains good covering property. Further, the electrode of the present invention is also superior in cycle characteristics because the cross-linked-type polyacrylic acid significantly increases binding strength between the active materials themselves or binding strength between the active material and the current collector, due to suitable cross-linking degree.
Thickness (thickness of the coating layer) of the active material layer is usually 1 to 500 μm, preferably 1 to 300 μm and more preferably 1 to 150 μm.
The electrode of the present invention can be produced in accordance with the method known per se, except for using the above-described composition for producing an electrode of the present invention, and it can be produced for example, by coating the above-described composition (which includes 1) the active material containing silicon, 2) the conductive assistant, and 3) the cross-linked-type polyacrylic acid) for producing an electrode pertaining to the present invention, on the current collector, drying, and then pressing. The composition for producing an electrode pertaining to the present invention is enough to be used in an amount for attaining the above-described thickness after drying. It should be noted that, in the case of using the compound shown by the general formula [12] or [13], or the polymer of the general formula [14], as the cross-linking agent of polyacrylic acid, the electrode of the present invention may be produced by coating a solution including polyacrylic acid and these cross-linking agents, instead of the cross-linked-type polyacrylic acid, onto the current collector, subjecting it to cross-linking on the current collector, drying and pressing. Or, cross-linking degree may be increased by coating the composition for producing an electrode including the cross-linked-type polyacrylic acid with lower cross-linking degree, onto the current collector, and making the cross-linking reaction promoted.
As a method for coating the composition for producing an electrode of the present invention, on the current collector, for example, an self-propelled coater, an ink jet method, a doctor blade method, a spray method, or a combination thereof can be used, and, a doctor blade method or an ink jet method, which can form a thin layer, is preferable, and a doctor blade method is more preferable.
Drying may be performed in accordance with a method known per se, and, it is performed usually by heating treatment. Drying condition (necessity of vacuum, drying time, drying temperature) in heating may be set appropriately depending on coating amount or volatilization speed of the composition for producing an electrode of the present invention.
Press method may also be performed in accordance with a method known per se, and, includes, for example, a calendar roll method, a flat plate press or the like, and a calendar roll method is preferable.
The above-described electrode of the present invention can be used in a lithium cell, and can be used in any of a usual cell as long as it is composed of a positive electrode, an electrolyte and a negative electrode.
As said electrolyte, the one having an additive such as vinylene carbonate, fluorovinylene carbonate, methylvinylene carbonate, fluoromethylvinylene carbonate, ethylvinylene carbonate, propylvinylene carbonate, butylvinylene carbonate, dipropylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4,5-diethylvinylene carbonate, vinylethylene carbonate, divinylethylene carbonate, phenylethylene carbonate, diallyl carbonate, fluoroethylene carbonate(FEC), catechol carbonate, 1,3-propane sultone, and butane sultone is preferable, and among them, the one having fluoroethylene carbonate (FEC) is particularly preferable. Content of the additives in the electrolyte is usually 0.5% to 15%, and preferably 0.5 to 5%.
Explanation will be given below in detail on the present invention with reference to Examples, however, the present invention should not be limited thereto.
(1) Synthesis of Polycarbodiimide (PCD)
PCD was synthesized according to the method described in the paper of J. Appl. Polym. Sci., 21, 1999 (1977). That is, a mixture of 5.00 g of tolylene-2,4-diisocyanate (28 mmol; produced by Tokyo Chemical Industry Co., Ltd.) and 50 mg of 3-methyl-1-phenyl-3-phospholene-1-oxide (produced by Tokyo Chemical Industry Co., Ltd.) (1.0% by mol to tolylene-2,4-diisocyanate) was refluxed in 20 mL of tetrahydrofuran (THF) under nitrogen for 2 hours at 80° C., and was subsequently filtered to remove indissolvable gel. The filtrate was dried under reduced pressure to remove the solvent. White powder obtained in this way was purified as below: (i) dissolving completely the powder into minimum amount of THF, (ii) pouring the THF solution into 1000 ml of hexane to precipitate a polymer, and (iii) filtering the polymer, picking it up and drying it under reduced pressure. After repeating this procedure (i) to (iii) twice, 1.03 g of white PCD powder was obtained finally (yield: 27%). In addition, molecular weight of the obtained PCD was 4000 in Mn (number average molecular weight), and 11000 in Mw (weight average molecular weight).
(2) Producing of Composition for Producing Electrode
Using a planet ball mill (Pulverisette 7, produced by Fristsch Inc.), 18 mg of nano-sized silicon powder (particle size: 100 nm, produced by Sigma-Aldrich Co. LLC.), 30 mg of natural graphite (particle size: 3 μm, produced by SEC Carbon Ltd.), and 6 mg of Ketjen Black (KB, produced by Lion Co.) were sufficiently mixed for 12 hours under 600 rpm. The obtained mixture (Si:graphite:KB=30:50:10, in weight ratio) was used as an electrode material. Next, polyacrylic acid (PAH, Mw=1250000, produced by Sigma-Aldrich Co. LLC.) was dissolved in N-methyl pyrrolidone (NMP). Into the above-described electrode material, firstly the NMP solution of PAH was added and mixed sufficiently, and it was further diluted with NMP to prepare slurry. Next, the NMP solution containing the predetermined amount of polycarbodiimide (PCD) was added to the slurry and mixed at room temperature for 20 minutes to produce slurry (composition) for producing three kinds of electrodes. In said slurry for producing the electrode, 18 mg of silicon, 30 mg of graphite and 6 mg of KB are included in 900 μL of the NMP solution. In addition, total amount of PAH and PCD in the slurry for producing three kinds of electrodes was set constant at 6 mg, and PCD amount was 0.3 mg, 0.6 mg and 0.9 mg, respectively, and PHA amount was 5.7 mg, 5.4 mg and 5.1 mg, respectively. That is, by coating the slurry for producing an electrode on the current collector, and then drying it, it became the one containing 30% by weight of silicon, 50% by weight of graphite, 10% by weight of KB, 0.95% by weight, 0.9% by weight or 0.85% by weight of PAH, and 0.5% by weight, 1.0% by weight or 1.5% by weight of PCD.
(3) Production of Negative Electrode for Lithium Cell
The above-described composition for producing an electrode was coated on a copper current collector using a doctor blade. After that, it was dried in air at 80° C. and then dried under vacuum at 150° C. for 24 hours. It should be noted that it was pressed using a roll before use to make an electrode. Thickness of a membrane on the current collector was about 9 to 10 μm by measurement using a micrometer (produced by Mitutoyo Corp.).
(4) Production of Coin-Type Cell
A coin-type cell was assembled in a glove box filled with argon. Here, a coin-type cell composed of the electrode obtained in (3), lithium foil electrode, an ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 in volume ratio) solution of 1 mol dm−3 LiPF6 and a separator, was assembled.
A composition for producing an electrode (a composition for producing an electrode including 10% by weight of PAH) was prepared by a similar method as in Example 1 (1) to (3), except for changing PCD concentration to 0% in Example 1 (2), to produce a negative electrode for a lithium cell (hereafter abbreviated as a lithium cell electrode (PAH) or Aldrich PAH).
A composition for producing an electrode was prepared similarly as in Comparative Example 1, and a lithium cell electrode was produced, except for using polyvinylidene fluoride (PVDF, produced by Polysciences Inc.), instead of polyacrylic acid in Comparative Example 1.
In order to examine a reaction between PAH and PCD, PAH and PCD were mixed in NMP at room temperature for 20 minutes, so as to attain the predetermined concentration [(a) PAH 10 wt %, PCD 0 wt %, (b) PAH 9.5 wt %, PCD 0.5 wt %, (c) PAH 9.0 wt %, PCD 1.0 wt %, and (d) PAH 5 wt %, PCD 5 wt %] (without using electrode materials such as the active material, the conductive assistant). Next, the NMP solution was cast on micro slide glass, dried similarly as in Example 1 (3) to prepare a cast film bound with a binder.
On the obtained 4 kinds of cast films (a) to (d), ATR-FTIR spectra were measured. Results thereof are described in
From this result, it was found that the carboxyl group was present in three different states, in PAH not containing PCD. That is, it was found that it was present in three different states of (i) a free carboxyl group (—COOH) at 1710 and 1410 cm−1, (ii) a carboxyl group associated by hydrogen bond at 1620 and 1460 cm−1 and (iii) a carboxylic anhydride group having C═O symmetric stretching and contraction at 1800 cm−1. These results show that main chains of PAH aggregated by formation of hydrogen bonds among partially dehydrated carboxyl groups, caused by drying in vacuum at 150° C. On the other hand, clear change was observed in IR spectrum of a cast film, when PCD is added into an NMP solution of PAH (when PAH forms a cross-linking structure). The IR peak of the carboxylic anhydride group became not observed when PCD concentration of (c) was 1.0% by weight, and formation of N-acyl urea (1650 cm−1) was confirmed when PCD concentration of (d) was 5.0% by weight. That is, with increase in the addition amount of PCD to PAH (with increase in cross-linking degree), absorption of the free carboxyl group became weak, and the carboxylic anhydride group disappeared in the IR spectrum, showing that all of the carboxyl groups react with sufficient amount of PCD. Accordingly, a chemically cross-linked structure of PAH by the addition of PCD was clarified from IR observation.
That is, it was found that cross-link bonding of PAH by the addition of PCD is generated by a cross-linking reaction with the carboxyl group in PAH, and hydrogen bond between the carboxyl groups is partially destroyed, resulting in dissociation of a PAH polymer aggregated in NMP. Accordingly, it is considered that slurry behaves suitable rheology, gives better dispersion between the active material and the conductive assistant, which gives influence on interaction between the carboxyl group and the active material.
(1) Measurement of 90 Degree Peeling Strength
On electrodes having PCD content of 1.0% by weight among electrodes obtained in Example 1 (3), and the electrode obtained in Comparative Example 1, a 90 degree peeling test was performed using a single column-type tensile-compression testing machine (STA-1150, produced by A&D Co., Ltd.).
As the result, peeling strength of the electrode having 1.0% by weight of PCD was 0.32 Ncm−1, and peeling strength of the electrode composed of polyacrylic acid was 0.04 Ncm−1, respectively.
That is, it was found that by cross-linking a polymer by the addition of PCD, peeling strength enhances largely.
In addition, it was also clarified that peeling strength of the electrode having 1.0% by weight of PCD is equal to or higher than peeling of the electrode.
(2) Comparison Between Image of an Optical Microscope and that of a Scanning Electron Microscope
Three kinds of electrodes obtained in Example 1 (3) and the electrode obtained in Comparative Example 1 were observed using an optical microscope having low magnification (50 times) and a scanning electron microscope having high magnification (10000 times) (SEM, SUPRA40, produced by Carl Zeiss AG). Images thereof were shown in
From this result, in PAH slurry not having PCD, a copper foil at the lower of the electrode layer was clearly observed using an optical microscope with a magnification of 50 times ((a) in
(3) Examination of Electrochemical Characteristics
Using three kinds of electrodes obtained in Example 1 (3) (the electrodes having a PCD content of 0.5% by weight, 1.0% by weight, and 1.5% by weight), and the electrode obtained in Comparative Example 1 (the electrode using not cross-linked polyacrylic acid as the binder), experiments were performed on characteristics of the initial charge-discharge, a differential capacity plot, and cycle characteristics. As for cycle characteristics, an experiment was performed also on the electrode obtained in Comparative Example 2 (using a vinylidene fluoride polymer as the binder).
Results (a charge-discharge curve of the first cycle) of initial charge-discharge, result of a differential capacity plot, and result of cycle characteristics are shown in
As shown in the above-described
From the differential dQ/dV plot in
As is clear from the result of
From the above-described results, it was found that by using the cross-linked-type polyacrylic acid as the binder, electrode performance of a silicon-based material can be enhanced largely. That is, by using the cross-linked-type polyacrylic acid, dispersion of the electrode material in slurry can be improved largely adjusting a polymer stereo-structure and rheology property of slurry in NMP. Further, chemical bonding by cross-linking of PAH suppresses distortion caused by volume expansion of silicon, and also improves stability of a composite electrode. Furthermore, the electrode having cross-linked PAH has good capacity retention, and can provide a reversible capacity of over 1000 mAh/g.
Accordingly, the cross-linked PAH exerts superior effect as the binder, and can widely apply to various electrode materials accompanying large volume change in charge-discharge.
(1) Production of Slurry for Producing of an Electrode
Using a planet ball mill (Pulverisette 7, produced by Fristsch Inc.), 0.3 g of silicon powder (particle size: <100 nm, produced by Sigma-Aldrich Co. LLC.), 0.5 g of natural graphite (particle size: 3 μm, produced by SEC Carbon Co., Ltd.), and 0.1 g of acetylene black (AB, produced by Strem Chemicals Inc.) were sufficiently mixed for 12 hours under 600 rpm. The obtained mixture (Si:graphite:AB=30:50:10, in weight ratio) was used as an electrode material. Next, using straight chain polyacrylic acid (produced by Wako Pure Chemical Industries, Ltd.), as the binder, 1 g of said polyacrylic acid (CLPHA-01) was dissolved in 99 g of ion exchanged water. Into 0.5 g of an aqueous solution of 1% by weight of polyacrylic acid, 0.045 g of the above-described electrode material was added and mixed sufficiently, and it was further diluted with ion exchanged water to prepare slurry. In said slurry for producing the electrode, 15 mg of silicon, 45 mg of graphite, 5 mg of AB and 5 mg of CLPHA-01 are included, respectively. That is, after coating said slurry for producing the electrode on the current collector, by drying it, it became to contain 30% by weight of silicon, 50% by weight of graphite, 10% by weight of AB and 10% by weight of polyacrylic acid.
(2) Producing of Electrode for Lithium Cell
The above-described slurry for producing an electrode was coated on a copper current collector using a doctor blade. After that, it was dried in air at 80° C. and then under vacuum at 150° C. for 24 hours. It should be noted that it was pressed using a roll before use to make an electrode (CLPAH-01 electrode). It should be noted that thickness of a membrane on the current collector was about 10 to 15 μm by observation using a composite beam process observation apparatus (JIB-4500, produced by JEOL Ltd.).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using Carbopol 980 (produced by Japan Chemicals Sales Co., Ltd.), instead of straight chain polyacrylic acid, instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as Carbopol electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-02) obtained by polymerization under containing of 0.007% by mol of diethylene glycol diallyl ether in the polymer, instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-02 electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-03) obtained by polymerization under containing of 0.07% by mol of diethylene glycol diallyl ether in the polymer, instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-03 electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-00) obtained by polymerization under containing of 0.7% by mol of diethylene glycol diallyl ether in the polymer, instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-00 electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-07) obtained by polymerization under containing of 0.14% by mol of diethylene glycol diallyl ether in the polymer instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-07 electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-11) obtained by polymerization under containing of 0.2% by mol of diethylene glycol diallyl ether in the polymer instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-11 electrode).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using cross-linked polyacrylic acid (CLPAH-14) obtained by polymerization under containing of 0.45% by mol of diethylene glycol diallyl ether in the polymer instead of the straight chain polyacrylic acid (hereafter this electrode is abbreviated as CLPAH-14 electrode).
Using the CLPAH-01 electrode, the CLPAH-02 electrode, the CLPAH-03 electrode, and the CLPAH-00 electrode, a constant current charge-discharge test was performed under the following condition.
Counter electrode: Li foil
Electrolytic solution: mixed solution of EC/DMC (1:1 in volume ratio) containing 1 M LiPF6
Measuring device: TOSCAT-3000U charge-discharge test equipment (produced by Toyo System Co., Ltd.)
Potential and current density
The first cycle
-
- Potential range 2.0 to 0.0 V (vs. Li/Li+)
- Current density 50 mAh/g
The 2nd and the subsequent cycle
-
- Potential range 2.0 to 0.0 V (vs. Li/Li+)
- Current density 100 mAh/g
Result of the initial charge-discharge, change of discharge capacity by charge-discharge cycle, change of coulombic efficiency by charge-discharge cycle, and change of coulombic efficiency by charge-discharge cycle (2nd to 10th), by each electrode are represented in
From the results of
In addition, as for reversible capacity during cycle, any of the electrodes using cross-linked PAH (hereafter they may be abbreviated as polyacrylic acid PAH electrodes) showed higher value, as compared with the not cross-linked straight chain PAH electrode (it may be abbreviated as the not cross-linked type PAH electrode; the CLAPA-01 electrode). In particular, it was found that the electrode using the CLAPA-03 electrode (an amount of the cross-linking agent, 0.07% by mol) shows very higher reversible capacity and capacity retention rate, as compared with other electrodes.
As for the initial coulombic efficiency, the binder using PAH having the higher cross-linking degree showed the higher value, although difference was very small. The not cross-linked-type PAH electrode (the CLPAH-01 electrode) showed lower value by 2 to 3%, as compared with the three cross-linked-type PAH electrodes.
In addition, as for coulombic efficiency from 2nd to 10th cycles [
It should be noted that when the result of the Aldrich electrode prepared similarly as in the CLPAH-01 electrode, using not cross-linked-type PAH, having a molecular weight of 1,250,000 (produced by Sigma-Aldrich Co. LLC.), is compared with the above-described result, it showed reversible capacity only about the same degree as that of the not cross-linked-type PAH electrode (the CLPAH-01 electrode), and largely lower reversible capacity, as compared with the CLPAH-03 electrode. Further, the initial coulombic efficiency was also the lowest among the four electrodes.
From these results, cross-linking of PAH is effective in improving electrochemical characteristics of the electrode, and among them optimum amount of the cross-linking agent of a polymer as the binder was estimated to be between CLPAH-02 (amount of the cross-linking agent, 0.007% by mol) and CLPAH-00 (amount of the cross-linking agent, 0.7% by mol), and around CLPAH-03 (amount of the cross-linking agent, 0.07% by mol).
Using the Aldrich electrode, the CLPAH-07 electrode, the CLPAH-11 electrode, the CLPAH-14 electrode, and the Carbopol electrode, a constant current charge-discharge test was performed similarly as in Experiment Example 3. As for result of the initial charge-discharge, result of the 10th time charge-discharge, and result of the 30th time charge-discharge, for each electrode, charge-discharge capacity thereof, coulombic efficiency and retention ratio thereof are shown in Table 1 below. In addition, results for the CLPAH-01 electrode, the CLPAH-02 electrode, the CLPAH-03 electrode, and the CLPAH-00 electrode (results of Experiment Example 3) are also shown together.
TABLE 1
Initial charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
Aldrich
straight chain
0
1495
971
65.0
—
CLPAH-01
straight chain
0
1495
1023
68.4
—
CLPAH-02
cross-linked
0.007
1379
972
70.5
—
CLPAH-03
cross-linked
0.07
1549
1098
70.8
—
CLPAH-07
cross-linked
0.14
1480
1076
72.7
—
CLPAH-11
cross-linked
0.2
1559
1096
70.3
—
CLPAH-14
cross-linked
0.45
1589
1122
70.6
—
CLPAH-00
cross-linked
0.7
1473
1046
71.0
—
Carbopol
cross-linked
—
1760
1128
64.1
—
10th time charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
Aldrich
straight chain
0
636
614
96.6
63.3
CLPAH-01
straight chain
0
647
626
96.7
61.2
CLPAH-02
cross-linked
0.007
733
708
96.6
72.9
CLPAH-03
cross-linked
0.07
974
942
96.7
85.8
CLPAH-07
cross-linked
0.14
897
867
96.6
80.5
CLPAH-11
cross-linked
0.2
827
797
96.3
72.7
CLPAH-14
cross-linked
0.45
796
765
96.1
68.1
CLPAH-00
cross-linked
0.7
786
761
96.8
72.7
Carbopol
cross-linked
—
759
731
96.3
64.8
30th time charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
Aldrich
straight chain
0
449
437
97.2
45.0
CLPAH-01
straight chain
0
468
455
97.4
44.5
CLPAH-02
cross-linked
0.007
507
492
97.1
50.6
CLPAH-03
cross-linked
0.07
703
679
96.5
61.8
CLPAH-07
cross-linked
0.14
639
618
96.7
57.4
CLPAH-11
cross-linked
0.2
566
548
96.8
50.0
CLPAH-14
cross-linked
0.45
543
525
96.6
46.8
CLPAH-00
cross-linked
0.7
577
560
97.0
53.5
Carbopol
cross-linked
—
504
489
97.1
43.4
From the results of Table 1, it was found that the initial discharge capacity shows a value near about 1000 mAh/g, in the case of using any electrode, regardless of cross-linking degree. However, the initial coulombic efficiency was around 65% in the not cross-linked-type PAH electrodes (the Aldrich electrode and the CLPA-01 electrode), or the electrode using a commercial Carbopol, while it was equal to or higher than 70% in the cross-linked-type PAH electrodes (CLAPA-02, 03, 07, 11, 14 and 00). From this result, it was found that the cross-linked-type PAH electrode of the present invention is capable of suppressing decomposition or the like of a solvent, not derived from a cell reaction.
In addition, it was found that charge-discharge capacity and retention ratio at the 10th and 30th cycle, in using the cross-linked-type PAH electrodes (CLPA-02, 03, 07, 11, 14, and 00), showed higher value, as compared with the not cross-linked-type PAH electrodes (the Aldrich electrode and the CLPA-01 electrode), or the Carbopol electrode.
From these results, it was found that use of cross-linked PAH as the binder enhances electrochemical characteristics of the electrode, as compared with the case of using the not cross-linked one. In addition, it was found that optimum amount of the cross-linking agent of a polymer as the binder is between CLPAH-02 (amount of the cross-linking agent, 0.007% by mol) and CLPAH-00 (amount of the cross-linking agent, 0.7% by mol), and particularly around CLPAH-03 (amount of the cross-linking agent, 0.07% by mol) is suitable.
Into 230 ml of water, 2.3 g of straight chain polyacrylic acid (produced by Wako Pure Chemical Industries, Ltd.) was added and dispersed by stirring for 2 hours. Into the obtained dispersed solution, 18% sodium hydroxide solution was added to adjust pH to 6.8 to obtain an aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAH0.2Na0.8-01).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-01 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (Aldrich0.2Na0.8) was obtained by similarly processing as in Comparative Example 5, except for using 2.3 g of polyacrylic acid produced by Sigma-Aldrich Co. LLC. (PAH, Mw=1250000, produced by Sigma-Aldrich Co. LLC.), instead of 2.3 g of straight chain polyacrylic acid (produced by Wako Pure Chemical Industries, Ltd.). Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the AldrichH0.2Na0.8 electrode.
An aqueous solution of 1% by weight of neutralized Carbopol (Carbopol H0.2Na0.8) was obtained by similarly processing as in Comparative Example 5, except for using 2.3 g of Carbopol 980 (produced by Japan Chemicals Sales Co., Ltd.), instead of 2.3 g of straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CarbopolH0.2Na0.8 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-02) was obtained by similarly processing as in Comparative Example 5, except for using 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.007% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. It should be noted that as diethylene glycol diallyl ether, the one synthesized in accordance with a method described in J. V. Crivello, S. K. Rajaraman, J. Polymer Science, Part A: Polymer Chemistry (1997), 35(8), 1593-1604 was used. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-02 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-03) was obtained by similarly processing as in Comparative Example 5, except for using 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.07% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-03 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-07) was obtained by similarly processing as in Comparative Example 5, except for using, 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.14% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-07 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-00) was obtained by similarly processing as in Comparative Example 5, except for using, 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.7% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-00 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-11) was obtained by similarly processing as in Comparative Example 5, except for using, 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.2% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-11 electrode.
An aqueous solution of 1% by weight of neutralized polyacrylic acid (CLPAHH0.2Na0.8-14) was obtained by similarly processing as in Comparative Example 5, except for using, 2.3 g of cross-linked polyacrylic acid obtained by polymerization under containing of 0.45% by mol of diethylene glycol diallyl ether in the polymer, instead of 2.3 g of the straight chain polyacrylic acid. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was referred to as the CLPAH0.2Na0.8-14 electrode.
A constant current charge-discharge test was performed similarly as in Experiment Example 3, except for using the CLPAH0.2Na0.8-01 electrode, the CLPAH0.2Na0.8-02 electrode, the CLPAH0.2Na0.8-03 electrode, and the CLPAH0.2Na0.8-07 electrode, as electrodes.
Result of the initial charge-discharge, change of discharge capacity by charge-discharge cycle, and change of coulombic efficiency by charge-discharge cycle by each electrode are shown in
From the results of
As for the initial coulombic efficiency, the binder having the higher cross-linking degree showed the higher value, although difference was small, and any of the cross-linked-type PAH electrodes showed higher value by about 5%, as compared with the CLPAH0.2Na0.8-01 electrode. In particular, the CLPAH0.2Na0.8-07 electrode also showed the highest initial coulombic efficiency. In addition, as for the 2nd time and the subsequent cycle, the CLPAH0.2Na0.8-02 electrode, and the 03 electrode showed a little faster rising, as compared with the CLPAH-01 electrode without cross-linking.
From these results, it can be said that means of neutralization, cross-linking or the like of a polymer are effective to improve electrochemical characteristics of the Si-based electrode. In particular, it was found that the CLPAH0.2Na0.8-07 showed superior effect as the binder.
A constant current charge-discharge test was performed similarly as in Experiment Example 3, except for using, as the electrode, the AldrichH0.2Na0.8 electrode, the CLPAH0.2Na0.8-11 electrode, the CLPAH0.2Na0.8-14 electrode, the CLPAH0.2Na0.8-00 electrode, or the Carbopol H0.2Na0.8 electrode.
As for result of the initial charge-discharge, result of the 10th time charge-discharge, and result of the 30th time charge-discharge, for each electrode, charge-discharge capacity, coulombic efficiency and retention ratio thereof are shown in the following Table 2. In addition, results for the CLPAH0.2Na0.8-01 electrode, the CLPAH0.2Na0.8-02 electrode, the CLPAH0.2Na0.8-03 electrode and the CLPAH0.2Na0.8-07 electrode (results of Experiment Example 5) are also shown together in Table 2.
TABLE 2
Initial charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
AldrichH0.2Na0.8
straight chain
0
1442
971
67.3
—
CLPAH0.2Na0.8-01
straight chain
0
1282
960
74.9
—
CLPAH0.2Na0.8-02
cross-linked
0.007
1416
1068
75.4
—
CLPAH0.2Na0.8-03
cross-linked
0.07
1351
1025
75.9
—
CLPAH0.2Na0.8-07
cross-linked
0.14
1446
1112
76.9
—
CLPAH0.2Na0.8-11
cross-linked
0.2
1542
1177
76.3
—
CLPAH0.2Na0.8-14
cross-linked
0.45
1535
1145
74.6
—
CLPAH0.2Na0.8-00
cross-linked
0.7
1387
1045
75.3
—
Carbopol ® H0.2Na0.8
cross-linked
—
1551
1076
69.4
—
10th time charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
AldrichH0.2Na0.8
straight chain
0
869
837
96.3
86.2
CLPAH0.2Na0.8-01
straight chain
0
840
815
97.0
84.9
CLPAH0.2Na0.8-02
cross-linked
0.007
1007
977
97.1
91.5
CLPAH0.2Na0.8-03
cross-linked
0.07
975
946
97.0
92.3
CLPAH0.2Na0.8-07
cross-linked
0.14
1094
1063
97.2
95.7
CLPAH0.2Na0.8-11
cross-linked
0.2
1165
1126
96.7
95.7
CLPAH0.2Na0.8-14
cross-linked
0.45
1071
1039
97.0
90.7
CLPAH0.2Na0.8-00
cross-linked
0.7
888
861
97.0
82.4
Carbopol ® H0.2Na0.8
cross-linked
—
840
813
96.9
75.6
30th time charge-discharge
Amount of
Charging
Discharging
cross-linking
capacity
capacity
coulombic
Retention
Type
agent mol %
(mAh/g)
(mAh/g)
efficiency %
rate %
AldrichH0.2Na0.8
straight chain
0
654
630
96.4
64.9
CLPAH0.2Na0.8-01
straight chain
0
594
575
96.8
59.9
CLPAH0.2Na0.8-02
cross-linked
0.007
751
724
96.3
67.8
CLPAH0.2Na0.8-03
cross-linked
0.07
715
688
96.3
67.1
CLPAH0.2Na0.8-07
cross-linked
0.14
849
816
96.2
73.4
CLPAH0.2Na0.8-11
cross-linked
0.2
891
851
95.5
72.3
CLPAH0.2Na0.8-14
cross-linked
0.45
824
792
96.2
69.2
CLPAH0.2Na0.8-00
cross-linked
0.7
659
635
96.4
60.8
Carbopol ® H0.2Na0.8
cross-linked
—
586
567
96.7
52.6
From the results of Table 2, it was found that by using the neutralized and cross-linked polymer, the initial coulombic efficiency value is enhanced, as compared with the not neutralized and cross-linked polymer. In addition, also as for charge-discharge at the 10th cycle, all of charge-discharge capacity, coulombic efficiency and retention ratio thereof are enhanced, and as for the 30th time cycle, although there was observed somewhat decrease in coulombic efficiency, it was found that charge-discharge capacity and retention ratio are enhanced.
In addition, as for the initial coulombic efficiency, the neutralized and cross-linked-type PAH electrodes (the CLPAH0.2Na0.8-02 electrode, -03 electrode, -07 electrode, -11 electrode, -14 electrode and -00 electrode) showed higher value by 5% or more, as compared with the neutralized AldrichH0.2Na0.8 electrode or the neutralized Carbopol electrode.
In addition, it was found that discharge capacity and retention ratio at the 10th and the 30th cycle are largely enhanced in many of the cross-linked-type PAH electrodes (the CLPAH0.2Na0.8-02 electrode, -03 electrode, -07 electrode, -11 electrode, and -14 electrode), as compared with the not cross-linked-type PAH electrode (CLPAH-01), and the electrode using Carbopol. In particular, the CLPAH0.2Na0.8-07 electrode and the CLPAH0.2Na0.8-11 electrode showed a discharge capacity at the 30th cycle of 800 mAh/g or higher, a retention ratio of 70% or higher, and the highest capacity retention. On the other hand, the CLPAH0.2Na0.8-14 electrode and the CLPAH0.2Na0.8-00 electrode, which used a large quantity of a cross-linking agent, had lower discharge capacity and retention ratio, as compared with the CLPAH0.2Na0.8-07 electrode and the CLPAH0.2Na0.8-11 electrode, and thus it was found that the more increased amount of the cross-linking agent does not necessarily enhances these values, and the case where an amount of the cross-linking agent of 0.1 to 0.3% by mol is most suitable for the binder.
From these results, it was found that neutralization and cross-linking of a polymer, in designing a binder, are effective to enhance electrochemical characteristics of the Si-based electrode. Among them, it was found that CLPAH0.2Na0.8-07 and CLPAH0.2Na0.8-11 show superior effect as the binder.
On CLPAH0.2Na0.8-07 and CLPAH0.2Na0.8-08, peeling strength was measured.
Firstly, an aqueous solution of polyacrylic acid containing 61 mg (solid content) of CLPAH0.2Na0.8-07 or CLPAH0.2Na0.8-08, and 450 mg of natural graphite (CGB-20) were mixed to prepare slurry for producing two kinds of electrodes for measuring peeling strength. Each of the obtained slurry was uniformly coated on a copper foil with a thickness of 10 μm, so as to attain a film thickness after drying of 100 μm, dried under vacuum at 130° C. for 2 hours, to prepare two kinds of electrodes for measurement of peeling strength.
A 180 degree peeling strength test was performed on the two kinds of electrodes (the electrode for measuring peeling strength of CLPAH0.2Na0.8-07, and the electrode for measuring peeling strength of CLPAH0.2Na0.8-08) in accordance with JIS K 6854-2. Specifically, by fixing a graphite side and peeling a copper foil, using a rigid adherent for the graphite side, and a flexible adherent for the copper foil side, a 180 degree peeling test was performed, in the following conditions.
Test piece: SUS (stainless steel) plate+double sided pressure sensitive adhesive tape+graphite layer/20 μm copper foil
Peeling width: 25 mm
Test condition: test speed; 100 mm/min, test temperature; 23° C.
Testing machine: Universal material testing machine, 5582-type, produced by Instron Japan Co., Ltd.
As the result, peeling strength of CLPAH0.2Na0.8-07 was 18.2 gf/mm, and peeling strength of CLPAH0.2Na0.8-08 was 15.7 gf/mm. In consideration of the result that peeling strength obtained by using a known functional group-containing vinylidene fluoride polymer is 3.8 gf/mm (JP Pat No. 4851092), it was found that the binder of the present invention shows binding strength equivalent to or higher than the above, and in particular, the neutralized binder can strongly bind to the electrode.
A coin-type cell was assembled in a glove box filled with argon. Specifically, a coin-type cell (without 2% FEC) was assembled using the CLPAH0.2Na0.8-03 electrode and a lithium foil electrode as an electrode, using a solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 in volume ratio) of 1 mol·dm−3 LiPF6 as an electrolytic solution, and using a micro-porous membrane made of a polyolefin as a separator.
In addition, a coin-type cell (with 2% FEC) of an FEC added electrolytic solution was also assembled similarly, except for using a mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 in volume ratio) of 1 mol·dm−3 LiPF6 and a fluoroethylene carbonate solution in 98:2, as an electrolytic solution.
Using the coin-type cell (without 2% FEC) and the coin-type cell (with 2% FEC), a charge-discharge test was performed similarly as in Experiment Example 3. It should be noted that as for the coin-type cell (with 2% FEC), result of a charge-discharge test, in the case where a charging time was 9 hours, is shown together.
Results thereof are shown in
From the results of
Slurry and the electrodes were observed with an optical microscope to examine influence of cross-linking of the binder on disperon property or coating property of slurry, and a surface state of the electrodes.
(1) Photographing of Slurry with an Optical Microscope
Firstly, each slurry of CLPAH-01, CLPAH0.2Na0.8-01, CLPAH-02, CLPAH0.2Na0.8-02, CLPAH-03, and CLPAH0.2Na0.8-03, obtained in producing various electrodes was diluted to 15 times with ion exchanged water. After that, each of the 50 μL of the obtained solution was dropped onto a preparate and covered with cover glass for observation with transmission light under a magnification of 50 times. It should be noted that as an apparatus for observation, Moticam 2300/2500 (produced by Shimadzu Rika Corp.) was used.
Results thereof are shown in
From the results of
In addition, in the PAH0.2Na0.8 type (neutralized type), there was observed little change of dispersion property of slurry by change of cross-linking degree, and any slurry showed better dispersion property, as compared with the PAH type.
(2) Photographing of the Electrode
In addition, after coating six kinds of slurry used in (1) onto a copper foil, and the dried one was subjected to photographing. The obtained results are shown in
From the results of
In the PAH0.2Na0.8 type, cross-linked CLPAH0.2Na0.8-03-02, and 03 showed a more uniformly coated state, as compared with not cross-linked CLPAH0.2Na0.8-01. The CLPAH0.2Na0.8 type showed more uniform coating with any binder, as compared with the PAH type.
(3) Photographing of the Electrode with an Optical Microscope
As for various the electrodes (the CLPAH-01 electrode, the CLPAH0.2Na0.8-01 electrode, the CLPAH-02 electrode, the CLPAH0.2Na0.8-02 electrode, the CLPAH-03 electrode, the CLPAH0.2Na0.8-03 electrode and the CLPAH-00 electrode), surfaces thereof were observed using reflection light under a magnification of 50 times. The obtained results are shown in
From the results of
In the PAH0.2Na0.8 type, the cross-linked CLPAH0.2Na0.8-02, and 03 electrodes had a more uniform surface state, as compared with the not cross-linked CLPAH0.2Na0.8-01 electrode. It should be noted that, as for the CarbopolH0.2Na0.8 electrode also, a photograph was taken using an optical microscope, and similarly as in the not cross-linked PAH type, there was a portion where a copper foil was observed, and thus was a not uniform surface form.
Accordingly, in consideration of other results together, it was considered that this uniform surface state and enhancement of dispersion property of slurry contribute to improvement of electrode characteristics.
(4) Observation of Electrode Cross-Section
As for various electrodes (the CLPAH-01 electrode, the CLPAH0.2Na0.8-01 electrode, the CLPAH-02 electrode, the CLPAH0.2Na0.8-02 electrode, the CLPAH-03 electrode, the CLPAH0.2Na0.8-03 electrode, and the CLPAH-00 electrode), after coating the electrode surface with carbon, using a composite beam fabrication observation apparatus (JIB-4500, produced by JEOL Ltd.), it was processed using FIB (ion source: gallium liquid metal ion source, acceleration voltage: 30 kV). The obtained electrode surface was observed using SEM.
As for observation result, result on the CLPA-type electrode is shown in
In the PVDF electrode of
In the PAH type, it was found that, although many large voids with a size of several μm were observed in the CLPAH-01 electrode having no cross-linking, in the CLPAH-03 electrode having increased cross-linking degree, such large voids decrease, and uniformity of the electrode enhances. In addition, in the CLPAH-00 electrode having further increased cross-linking degree, large voids were observed again inside the electrode.
In the PAH0.2Na0.8 type, large cracks w ere decreased in any cross-linking degree, as compared with PAH. In addition, the PAH0.2Na0.8 electrode of CLPAH-03 had a porous structure. Such a porous structure has been known to mitigate influence of volume change in the silicon-based electrode, and is effective to enhance cycle characteristics. Accordingly, reason for the PAH0.2Na0.8-03 electrode to show high cycle characteristics is considered to be related to such a uniform and porous electrode structure.
Fluidity of the binders used in various electrodes was measured.
Specifically, flow curve measurement was performed using HAAKE MARS III (produced by Thermo Scientific Co., Ltd.) to measure fluidity of each aqueous solution of 1% by weight of polyacrylic acid of CLPAH-01, CLPAH-02, CLPAH-03, CLPAH0.2Na0.8-01, CLPAH0.2Na0.8-02, and CLPAH0.2Na0.8-03. That is, after coating an aqueous solution of 1% by weight of polyacrylic acid on to a sample stand with a diameter of 35 mm, so as to attain each uniform thickness, a sensor was descended so as to attain a distance of 0.3 mm between the sample stand and the sensor. During the measurement, temperature was maintained at 20° C., and range of sheer rate at 0.01 to 1833 s−1, to measure in 100 steps.
Results thereof are shown in
The horizontal axis of the graph in
In CLPAH-01 to 03, there is proportional relationship between sheer stress and sheer rate, and viscosity is constant regardless of sheer rate. Such flow is called Newtonian flow, and water or low viscosity silicon oil and the like shows this type of flow. Reason for not a good coating state of the CLPA binder, as shown in
A coating liquid usually has property that apparent viscosity decreases with increase in sheer rate, and this phenomenon is called thixotropy. This tendency is observed also in an aqueous starch solution or latex. PAH of Aldrich and PAH0.2Na0.8 of Aldrich, shown in
From
From various polyacrylic acids (AldrichH0.2Na0.8, CLPAH0.2Na0.8-01, CLPAH0.2Na0.8-02, CLPAH0.2Na0.8-03, CLPAH0.2Na0.8-07, CLPAH0.2Na0.8-11, CLPAH0.2Na0.8-14, CLPAH0.2Na0.8-00, or Carbopol H0.2Na0.8), 1% by weight of polyacrylic acid slurry was prepared, to measure viscosity thereof at 20° C. using a B-type viscometer (88 L, produced by Tokyo Keiki Co., Ltd.). As rotation speed, values described in Table 3 were used in response to a kind of polyacrylic acid.
TABLE 3
Amount of
cross-linking
Viscosity
Viscosity
Type
agent mol %
0.6 rpm mPa · s
60 rpm mPa · s
AldrichH0.2Na0.8
straight chain
0
—
6,050
CLPAH0.2Na0.8-01
straight chain
0
—
21
CLPAH0.2Na0.8-02
cross-linked
0.007
—
44
CLPAH0.2Na0.8-03
cross-linked
0.07
—
75
CLPAH0.2Na0.8-07
cross-linked
0.14
—
272
CLPAH0.2Na0.8-11
cross-linked
0.2
—
1,430
CLPAH0.2Na0.8-14
cross-linked
0.45
367,000
—
CLPAH0.2Na0.8-00
cross-linked
0.7
709,300
—
Carbopol H0.2Na0.8
cross-linked
—
494,000
—
From the results of Table 3, it was found that with increase in amount of the cross-linking agent, viscosity increases. As for cross-linked polyacrylic acid, lower limit of viscosity thereof was 30 mPa·s at the least under a rotation speed of 60 rpm, and upper limit of viscosity thereof was 800000 mPa·s at least under a rotation speed of 0.6 rpm. In addition, from the result of Experiment Example 6 (Table 2), it was found that the CLPAH0.2Na0.8-07 electrode and the CLPAH0.2Na0.8-11 electrode are preferable as the binder, and in the CLPAH0.2Na0.8-00 electrode, effect thereof is a little weakened, therefore, preferable viscosity range thereof was considered to be from 30 mPa·s to 10000 mPa·s of the upper limit of the apparatus at 60 rpm, and from 10000 mPa·s of the lower limit of the apparatus to 450000 mPa·s at 0.6 rpm.
Using the CLPAH-01 electrode, the CLPAH-02 electrode, and the CLPAH-03 electrode, a self-discharge test was performed. That is, after charging at the 12th cycle, they were left to stand for 10 days in a fully charged state, and charging was performed again to perform a charge-discharge test at that time. Specifically, a constant current charge-discharge test was performed under the following condition. The obtained result is shown in
In addition, using the CLPAH0.2Na0.8-01 electrode, the CLPAH0.2Na0.8-02 electrode, and the CLPAH0.2Na0.8-03 electrode as the electrode, a constant current charge-discharge test was performed under the following condition similarly. The result obtained is shown in
[Measurement Condition]
Working electrode: Si(<100 nm): SNO3:AB:binder=3:5:1:1 electrode
Counter electrode: Li foil
Electrolytic solution: EC/DMC (1:1 in volume ratio) solution containing 1 M LiPF6
Constant current charge-discharge test
The first cycle (CC)
Potential range 2.0 to 0.0 V (vs. Li/Li+)
Current density 50 mAh/g
The 2nd and the subsequent cycle
Potential range 2.0 to 0.0 V (vs. Li/Li+)
Current density 100 mAh/g
It should be noted that, after fully charging at the 12th cycle, they were left to stand for 10 days, and then charge-discharge was performed for further 5 cycles (from the 13th to the 17th cycles).
From the results of
Slurry for producing an electrode was prepared similarly as in Example 9, except for using 0.3 g of silicon powder having a particle size of 5 μm, instead of 0.3 g of silicon powder with a particle size of less than 100 μm, to produce the electrode for a lithium cell (hereafter this electrode is abbreviated as the 5μ Si-CLPAH0.2Na0.8-03 electrode).
A constant current charge-discharge test was performed under the following condition, except for using the 5μ Si-CLPAH0.2Na0.8-03 electrode obtained in Example 15, and changing potential range from 2.0 to 0.0 V to 1.0 to 0.0 V.
Counter electrode: Li foil
Electrolytic solution: EC/DMC mixed solution (1:1 in volume ratio) containing 1 M LiPF6
Measuring device: TOSCAT-3000U charge-discharge test equipment (produced by Toyo System Co., Ltd.)
Potential and current density
The first cycle
Potential range 1.0 to 0.0 V (vs. Li/Li+)
Current density 50 mAh/g
The 2nd and the subsequent cycle
Potential range 1.0 to 0.0 V (vs. Li/Li+)
Current density 100 mAh/g
Results thereof are shown in
From the results of
In
An aqueous solution of 1% by weight of neutralized polyacrylic acid was obtained by similarly experimenting as in Comparative Example 5, except for using, instead of 2.3 g of the straight chain polyacrylic acid, 2.3 g of 6 kinds of cross-linked polyacrylic acids obtained by cross-linking under containing of 0.14% by mol of any of the 6 kinds of cross-linking agents described in the following Table 4, in polyacrylic acid, instead of 2.3 g of straight chain polyacrylic acids. Next, slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using each solution, instead of the aqueous solution of 1% by weight of polyacrylic acid, to produce 6 kinds of electrodes for a lithium cell.
It should be noted that as for diethylene glycol diacrylate in the Table, the one synthesized in accordance with a method described in B. H. Kim, E. J. Jeong, G. T. Hwang, N. Venkatesan, Synthesis (2001), 14, 2191-2202 was used. In addition, as for ethylene glycol diallyl ether and tetraethylene glycol diallyl ether, those synthesized in accordance with a method described in J. V. Crivello, S. K. Rajaraman, J. Polymer Science, Part A: Polymer Chemistry (1997), 35(8), 1593-1604 were used.
TABLE 4
Cross-linking agent
Structural formula
Electrode Name
methylenebisacrylamide (produced by Wako Pure Chemical Industries, Ltd.)
##STR00049##
CLPAH0.2Na0.8—C1 Electrode
1,5-hexadiene-3,4-diol (produced by Tokyo Chemical Industries, Ltd.)
##STR00050##
CLPAH0.2Na0.8—C2 Electrode
divinyl benzene (produced by Wako Pure Chemical Industries, Ltd.)
##STR00051##
CLPAH0.2Na0.8—C3 Electrode
pentaerythritol triallyl ether (produced by Daiso Co., Ltd.)
##STR00052##
CLPAH0.2Na0.8—C4 Electrode
diethylene glycol diacrylate
##STR00053##
CLPAH0.2Na0.8—C5 Electrode
ethylene glycol diallyl ether
##STR00054##
CLPAH0.2Na0.8—C6 Electrode
tetraethylene glycol diallyl ether
##STR00055##
CLPAH0.2Na0.8—C7 Electrode
A constant current charge-discharge test was performed similarly as in Experiment Example 4, except for using the CLPAH0.2Na0.8—C1 electrode, the CLPAH0.2Na0.8—C2 electrode, the CLPAH0.2Na0.8—C3 electrode, the CLPAH0.2Na0.8—C4 electrode, the CLPAH0.2Na0.8—C5 electrode, the CLPAH0.2Na0.8—C6 electrode, and the CLPAH0.2Na0.8—C7 electrode, as the electrode.
As for result of the initial charge-discharge and result of the 10th time charge-discharge using each electrode, charge-discharge capacity, coulombic efficiency and retention ratio thereof are shown in the following Table 5. It should be noted that, as reference, results of the CLPAH0.2Na0.8-07 electrode and the Carbopol H0.2Na0.8 electrode are shown together in Table 5.
TABLE 5
Initial charge-discharge
10th time charge-discharge
Charging
Discharging
Charging
Discharging
capacity
capacity
coulombic
capacity
capacity
coulombic
Retention
No.
(mAh/g)
(mAh/g)
efficiency %
(mAh/g)
(mAh/g)
efficiency %
rate %
CLPAH0.2Na0.8-C1
1381
1042
75.5
967
932
96.4
89.4
CLPAH0.2Na0.8-C2
1570
1124
71.6
1118
1075
96.2
95.6
CLPAH0.2Na0.8-C3
1358
1030
75.8
964
930
96.5
90.3
CLPAH0.2Na0.8-C4
1489
1107
74.3
1064
1025
96.3
92.6
CLPAH0.2Na0.8-C5
1505
1120
74.4
1052
1020
97.0
91.1
CLPAH0.2Na0.8-C6
1534
1135
74.0
1080
1045
96.8
92.1
CLPAH0.2Na0.8-C7
1484
1125
75.8
1088
1055
97.0
93.8
CLPAH0.2Na0.8-07
1446
1112
76.9
1094
1063
97.2
95.7
Carbopol H0.2Na0.8
1551
1076
69.4
840
813
96.9
75.6
From the results of Table 5, it was found that the initial discharge capacity showed a value near about 1100 mAh/g not depending on a kind of the cross-linking agent. In addition, coulombic efficiency was 70% or higher, and it was high value in any of them, as compared with the electrode using Carbopol. In addition, discharge capacity or retention ratio at the 10th cycle became about 1000 mAh/g and about 90%, respectively, not depending on a kind of a cross-linking agent, and it was very high value, as compared with the electrode using Carbopol. In particular, the CLPAH0.2Na0.8—C2 electrode, the CLPAH0.2Na0.8—C4 electrode, the CLPAH0.2Na0.8—C5 electrode, the CLPAH0.2Na0.8—C6 electrode, and the CLPAH0.2Na0.8—C7 electrode showed high capacity retention rate equivalent to that of the CLPAH0.2Na0.8-07 electrode, as for discharge capacity or retention ratio at the 10th cycle.
From these results, it was shown that means of neutralization, and cross-linking of a polymer, in designing a binder, are effective to enhance electrochemical characteristics of the Si-based electrode.
Various polyacrylic acids (CLPAH0.2Na0.8—C1 to CLPAH0.2Na0.8—C7) were converted to 1% by weight polyacrylic acid slurry, to measure viscosity at 20° C. using a B-type viscometer (B8L, produced by Tokyo Keiki Co., Ltd.). Rotation speed was set at 60 rpm in measurement. The result thereof is shown in the following Table 5.
TABLE 6
Amount of
cross-linking
Viscosity 60 rpm
No.
Type
agent (mol %)
(mPa · s)
CLPAH0.2Na0.8-C1
cross-linked
0.14
960
CLPAH0.2Na0.8-C2
cross-linked
0.14
70
CLPAH0.2Na0.8-C3
cross-linked
0.14
240
CLPAH0.2Na0.8-C4
cross-linked
0.14
230
CLPAH0.2Na0.8-C5
cross-linked
0.14
300
CLPAH0.2Na0.8-C6
cross-linked
0.14
250
CLPAH0.2Na0.8-C7
cross-linked
0.14
320
From the results of the above-described Table 6, it was found that viscosity value differs depending on a kind of a cross-linking agent, however, any polymers have viscosity within a preferable range shown in the above-described Table 3.
Into 230 mg of water, 2.3 g of cross-linked polyacrylic acid, obtained by cross-linking and polymerization by containing 0.14% by mole of diethylene glycol diallyl ether in straight chain cross-linked-type, was added and dispersed under stirring for 2 hours. Into the obtained dispersed solution, 4.5 ml of 17% sodium hydroxide was added to obtain an aqueous solution of 1% by weight neutralized polyacrylic acid (CLPAH0.3Na0.7-01).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution instead of the aqueous solution of 1% by weight polyacrylic acid, to produce the electrode for a lithium cell. The obtained electrode was named as the CLPAH0.3Na0.7-07 electrode.
Into 230 mg of water, 2.3 g of cross-linked polyacrylic acid, obtained by cross-linking and polymerization by containing 0.14% by mole of diethylene glycol diallyl ether in straight chain cross-linked-type, was added and dispersed under stirring for 2 hours. Into the obtained dispersed solution, 5.7 ml of 17% sodium hydroxide was added to obtain an aqueous solution of 1% by weight neutralized polyacrylic acid (CLPAH0.1Na0.9-01).
Slurry for producing an electrode was prepared similarly as in Comparative Example 3, except for using said solution instead of the aqueous solution of 1% by weight polyacrylic acid, and the electrode obtained by producing the electrode for a lithium cell was referred to as the CLPAH0.1Na0.9-07 electrode.
A constant current charge-discharge test was performed similarly as in Experiment Example 4, except for using the CLPAH0.3Na0.7-07 and CLPAH0.1Na0.9-07 electrodes, as the electrode.
As for result of the initial charge-discharge and result of the 10th time charge-discharge using each electrode, charge-discharge capacity, coulombic efficiency and retention ratio thereof are shown in the following Table 7. It should be noted that, as reference, results of the CLPAH0.2Na0.8-07 electrode are shown together in Table 7.
TABLE 7
Initial charge-discharge
10th time charge-discharge
Charging
Discharging
Charging
Discharging
Neutralization
capacity
capacity
coulombic
capacity
capacity
coulombic
Retention
No.
degree
(mAh/g)
(mAh/g)
efficiency %
(mAh/g)
(mAh/g)
efficiency %
rate %
CLPAH0.3Na0.7-07
70%
1453
1100
75.7
1083
1048
96.8
95.3
CLPAH0.2Na0.8-07
80%
1446
1112
76.9
1094
1063
97.2
95.7
CLPAH0.1Na0.9-07
90%
1476
1122
76.0
1084
1051
97.0
93.7
From the results of Table 7, the initial discharge capacity and discharge capacity or retention ratio at the 10th cycle showed similar behavior not depending on degree of neutralization. Among them, the result in the case of degree of neutralization of 80% showed the slightly highest value. Accordingly, it was found that good electrical characteristics can be obtained, as long as it is a cross-linked PAH having degree of neutralization of 70 to 90%.
Each of two kinds of polyacrylic acids (CLPAH0.3Na0.7-07 and CLPAH0.1Na0.9-07) was converted to 1% by weight poly acrylic acid slurry, to measure viscosity at 20° C. using a B-type viscometer (B8L, produced by Tokyo Keiki Co., Ltd.). Rotation speed was set at 60 rpm in measurement. The result thereof is shown in the following Table 8.
TABLE 8
Amount of
cross-linking
Neutralization
Viscosity 60 rpm
No.
agent (mol %)
degree
(mPa · s)
CLPAH0.3Na0.7-07
0.14
70
250
CLPAH0.2Na0.8-07
0.14
80
272
CLPAH0.1Na0.9-07
0.14
90
220
It was found that there is no big change of viscosity, although it was some difference, depending on degree of neutralization.
Hashimoto, Shota, Sasaki, Takeo, Komaba, Shinichi, Maesawa, Tsuneaki, Okamoto, Kuniaki, Yabuuchi, Naoaki, Han, Zhen-ji
| Patent | Priority | Assignee | Title |
| 12107207, | Sep 29 2017 | PROLOGIUM TECHNOLOGY CO , LTD ; PROLOGIUM HOLDING INC | Flexible battery |
| Patent | Priority | Assignee | Title |
| 3948867, | Jul 03 1970 | Deutsche Gold- und Silber-Scheideanstalt vormals Roessler | Process for polymerizing acrylic acid with inhibitor and retarder present and the use of resultant polyacrylic acids |
| 4963447, | Feb 08 1990 | Matsushita Electric Industrial Co., Ltd.; Nihon Junyaku Co., Ltd. | Alkaline cell with gelled anode |
| 6194512, | Jun 28 1999 | Owens Corning Intellectual Capital, LLC | Phenol/formaldehyde and polyacrylic acid co-binder and low emissions process for making the same |
| 20030149227, | |||
| 20070092796, | |||
| 20080103248, | |||
| 20120070737, | |||
| 20120189861, | |||
| 20140234246, | |||
| 20140322321, | |||
| 20150132550, | |||
| 20160369210, | |||
| JP2000294247, | |||
| JP2006339093, | |||
| JP2009140918, | |||
| JP200980971, | |||
| JP201264574, | |||
| JP2014530827, | |||
| JP2015500264, | |||
| JP2016530351, | |||
| JP4851092, | |||
| JP9289022, | |||
| WO2011122261, | |||
| WO2012161096, |
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